CN100484985C - Conductive polyanion/starch shell-core type composite microsphere and its preparation method - Google Patents
Conductive polyanion/starch shell-core type composite microsphere and its preparation method Download PDFInfo
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Abstract
The invention discloses a conductive polyaniline/starch case karyotype composite microball and preparing method, which is characterized by the following: (1) allocating starch solution; (2) preparing colloidal particle of starch nanometer; decorating colloidal particle surface physically; (3) adding phenylamine monomer; (4) triggering to polymerize for oxidant.
Description
Technical field
The present invention relates to conductive polyanion/starch shell-core type composite microsphere and preparation method thereof, being particularly related to the starch nano micelle is the preparation method of the polyanion/starch shell-core type composite microsphere of polymerizing template, belongs to the interdisciplinary field of macromolecular material and nano composite material.
Background technology
The matrix material of nucleocapsid structure becomes a focus of material area research because its unique character more and more causes concern widely.Along with material constantly develops to the functionalization direction, the novel material that relates to different structure and performance becomes the focus of concern day by day, and the matrix material of nucleocapsid structure has been complied with this trend just, and people can be designed its structure and application performance on the both macro and micro yardstick.People expect that this type of material fully develops talents at high-technology fields such as biology, medicine, materials.
In numerous conductive polymerss, the polyaniline raw material is easy to get, synthesizes simple, and not only have good electrical conductivity, and good environmental stability is arranged, be a kind of application prospect electro-conductive material preferably.But because the strong rigidity of polyaniline chain and the solvability extreme difference that the interchain strong interaction makes it, the performance that this has greatly influenced it has limited its range of application.Though can adopt macromolecule organic acid " auto-doping ", alkyl or alkane that aniline monomer carries out on the phenyl ring are supported the base replacement, and carry out monomeric grafting and block copolymerization modification, blend, many methods such as compound, but often to reduce specific conductivity simultaneously, or increase the cost and the difficulty of processing of processing units.In recent years, adopt new polymerization technique to prepare the polyaniline latex beads of micro nano structure, it is higher to obtain specific conductivity, being convenient to the micro-nano phase conducting polymer composite of actual industrial processing and the various special construction types of using, morphological specificity, performance etc. again, is a kind of effective ways that improve Polyaniline Processability.Typical the synthetic of polyaniline latex beads is that monomer carries out chemical oxidising polymerisation in the presence of water-soluble steric stabilizer, and steric stabilizer can stop attracting each other of polymerisate and aggregate and precipitate.Coating one deck conductive polymers on the polymer billet surface, prepare hud typed complex microsphere, is stability and the size of control microballoon and a kind of good method of pattern that increases complex microsphere.Complex microsphere can be taken into account two kinds of properties of materials, can make up for each other's deficiencies and learn from each other on performance, produces synergistic effect, can give mixture different characteristics with shell by choosing corresponding kernel, thereby satisfy various requirement.
U.S. Pat 20030065090, title are that " Polyaniline coating compsition " discloses a kind of preparation method who is used for the polyaniline composite particles of coating composition, and wherein the kernel of composite particles is the polymkeric substance that contains strong acid group.This mixture is to contain the polymkeric substance ball milling granulation of acidic-group, and the monomer emulsion polymerization that maybe will contain acidic-group prepares the polymkeric substance kernel, separates, purifies, and adds aniline monomer and initiator more successively and carries out polymerization.But; the interior nuclear monomer that this preparation method chooses must contain specific acidic-group; in the kernel preparation, need loaded down with trivial details aftertreatment simultaneously; this can destroy the morphological structure of polymkeric substance kernel to a certain extent; simultaneously increase reactions steps and tooling cost especially, be unfavorable for being extended to the industrial use of mass-producing.
Starch is distributed widely in nature as a kind of natural polymer, and renewable, biodegradable, price is low, and Application Areas has in recent years obtained bigger expansion.World patent WO0040617, title is " Method for the preparation of starch particles ", adopt the reverse microemulsion liquid system, Zulkovsky starch is dissolved in aqueous phase, add linking agent, the starch molecule of dissolved state is cross-linked into tiny microballoon and separates out from liquid phase, thereby obtains the micro/nano level spherex.But complex process, influence factor is more, and preparation that must spherex improves, and just can well be used.
In conjunction with above 2 points, this just presses for a kind of preparation method of novelty, adopt the raw material of wide material sources, and with the preparation of polymkeric substance kernel, the finishing of kernel, and the coating of polyaniline combines, reaction is carried out continuously, both simplified experimental procedure, can reduce the negative impact of sepn process again product pattern and performance.
Summary of the invention
The object of the present invention is to provide a kind of conductive polyanion/starch shell-core type composite microsphere and preparation method thereof.Disperse polymerization technique to combine the preparation of starch nano micelle, finishing and precipitation, have that raw material sources are extensive, working method is simple, the characteristics of preparation size and controllable structure.
Conductive polyanion/starch shell-core type composite microsphere kernel of the present invention is a natural polymer starch, shell is a conductive polymer polyanilinc, and starch is covered by the inside of electrically conductive polyaniline, forms the core-shell type complex microsphere, this complex microsphere particle diameter is in 50 nanometers～5 micron, and room-temperature conductivity is 1.5 * 10
-5～1.6S/cm.
The preparation method of conductive polyanion/starch shell-core type composite microsphere of the present invention is characterized in that comprising step:
(1) preparation starch nano micelle: get a certain amount of starch solution, under high speed machine stirring and ultra-sonic dispersion situation, dropwise join in the water/alcohol mixeding liquid that contains anion surfactant;
(2) preparation aniline/doping agent aqueous solution, and join in the starch nano micelle system of step (1) preparation;
(3) to the hanging drop oxidizer aqueous solution of step (2) preparation, at room temperature initiated polymerization obtains described conductive polyanion/starch shell-core type composite microsphere.
The solvent that step 1 preparation starch solution uses is dimethyl sulfoxide (DMSO), N, dinethylformamide, N, the mixed solution of N-N,N-DIMETHYLACETAMIDE or above-mentioned solvent and deionized water, the massfraction of starch is 5%～35% in the solution, stirs down at 40 ℃～90 ℃ and makes it whole dissolvings.
The volume ratio of step 1 starch solution and water/alcohol mixeding liquid is 1:10～20, anion surfactant is Witco 1298 Soft Acid and metal-salt, hexadecyl Phenylsulfonic acid and metal-salt, naphthene sulfonic acid and metal-salt thereof or sodium lauryl sulphate, the volume ratio of dehydrated alcohol and deionized water is 1:1.5～9 in water/alcohol mixeding liquid, and churned mechanically speed is 1000～1500 rev/mins.
Step 2 doping agent is mineral acid example hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, nitric acid, or organic acid such as acetic acid, tosic acid, and the pH value of system is 0～3.
Step 3 oxygenant is ammonium persulphate, hydrogen peroxide, potassium bichromate, potassium hypochlorite, clorox or iron(ic) chloride, and polymerization temperature is 5～30 ℃, and polymerization time is 5～24 hours, and the mol ratio of aniline monomer and oxygenant is 1:1～2.
Below in conjunction with reaction mechanism figure (1), technical scheme of the present invention is further set forth: the present invention adopts raw material sources starch widely, utilize the solvability characteristics, under the condition of high speed machine stirring and ultra-sonic dispersion, prepared the starch micelle of micro nano structure.Then the starch nano micelle with preparation is a polymerizing template, characteristic according to tensio-active agent is carried out physical modification to the starch particle surface, make it coat one deck negative charge layer, according to electrostatic adhesion mechanism, at nanoparticle surface adsorption of aniline monomer, disperse polymerization technique to prepare the complex microsphere of polyaniline/starch with core-shell structure in conjunction with precipitation.Have functions such as electromagnetic shielding, antistatic coating, anti-corrosion of metal, plastics additive and drug molecule carrier.
Starch is difficult to be dissolved in fully deionized water under the normal temperature, the solvent that the preparation starch solution uses is dimethyl sulfoxide (DMSO), N, the mixed solution of dinethylformamide, N-N N,N-DIMETHYLACETAMIDE or above-mentioned solvent and deionized water, the massfraction of starch is 5%～35% in the solution, stirs down at 40 ℃～90 ℃ and makes it whole dissolvings.
The preparation of starch nano micelle has utilized the solvability characteristics of starch, adopt Witco 1298 Soft Acid and metal-salt, hexadecyl Phenylsulfonic acid and metal-salt thereof or naphthene sulfonic acid and metal-salt thereof, sodium lauryl sulphate as anion surfactant, water/alcohol mixed solution is as the precipitation agent of starch, in the disposable adding reactor, the volume ratio of dehydrated alcohol and deionized water is 1:1.5～9.5 in water/alcohol mixeding liquid.With a certain amount of starch solution, high speed machine stir and the situation of ultra-sonic dispersion under, dropwise add slowly contain negatively charged ion and show promoting agent during water/ethanol mixing is molten.Churned mechanically speed is 1000～1500rpm, and drop rate is 1 droplet/minute, and the mass ratio of anion surfactant and starch is 1:5～15.Anion surfactant in the mixed solution is adsorbed on the surface of starch milk micelle, has played and has avoided the stabilization of reuniting, and the negative charge layer of Xing Chenging provides condition for the preparation of polyanion/starch shell-core type composite microsphere simultaneously.
The method of the complex microsphere of preparation core-shell type polyaniline/starch, aniline monomer is dissolved in the doping aqueous acid, the dopant acid that is adopted can be mineral acid example hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, nitric acid, or organic acid such as acetic acid, tosic acid, and the pH value of regulation system is 0～3.H in monomer and the mixed solution
+Formed the aniline positive ion, with the starch milk micelle generation electrostatic adsorption of electronegative layer.After adsorption equilibrium after a while, the aqueous solution initiated polymerization that adds oxygenant again, oxygenant can be ammonium persulphate, hydrogen peroxide, potassium bichromate, potassium hypochlorite, clorox, iron(ic) chloride, polymerization temperature is 5～30 ℃, polymerization time is 5～24 hours, the mol ratio of aniline monomer and oxygenant is 1:1～2, obtains having the polyaniline/composites of starch microballoon of core-shell structure.
The present invention disperses polymerization technique to combine preparation, finishing and the precipitation of starch nano micelle, utilize the solvability characteristics of starch to prepare the starch micelle, prevent the anion surfactant that the starch micelle is reunited, also played monomeric electrostatic adsorption, for favourable condition has been created in follow-up polymerization, anion surfactant has been removed the loaded down with trivial details step of aftertreatment from again as the doping agent of polyaniline simultaneously.Two-step reaction carries out continuously, has both simplified experimental procedure, can reduce the negative impact of sepn process to the product pattern again.The invention provides the method for the electrically conductive polyaniline-starch shell caryogram complex microsphere of a kind of raw material sources are extensive, working method is simple preparation size and controllable structure, can well be applied to fields such as electromagnetic shielding, antistatic coating, protective system, electrorheological fluid and drug molecule carrier.
Description of drawings
Fig. 1: the reaction mechanism figure of preparation conductive polyanion/starch shell-core type composite microsphere;
Fig. 2: the transmission electron microscope photo of polyanion/starch shell-core type composite microsphere (scale is 200 nanometers among the figure)
Embodiment
Embodiment 1
0.1 gram starch places the 10ml dimethyl sulfoxide (DMSO), 60 ℃ of lower magnetic force stirring and dissolving.Starch solution slowly is added dropwise to the 100ml deionized water/alcohol mixed solution that contains 0.03 gram Witco 1298 Soft Acid, and (alcohol: water=1:9), 1000 rev/mins of churned mechanically speed, drop rate are 1 droplet/minute.The aniline of 2.5mmol is dissolved in the 20ml 0.1mol/L hydrochloric acid soln, and the disposable suspension that joins the starch nano micelle that had before made is regulated pH value about 0-1 with hydrochloric acid.The 2.5mmol ammonium persulphate is dissolved in the 20mL deionized water, slowly is added dropwise in the system, be controlled at and dropwised in 40 minutes, temperature of reaction about 5 ℃, sustained reaction 12 hours.Add the acetone termination reaction, use acetone, distilled water repetitive scrubbing respectively, use the sand core funnel suction filtration,, obtain blackish green product at 60 ℃ of vacuum-drying 24h.The median size of complex microsphere is in 300 nanometers, and room-temperature conductivity is 0.52S/cm.
Embodiment 2
0.2 gram starch places 10ml N, in the dinethylformamide, 80 ℃ of lower magnetic force stirring and dissolving.Starch solution slowly is added dropwise to the 100ml deionized water/alcohol mixed solution that contains 0.035 gram hexadecyl Phenylsulfonic acid, and (alcohol: water=2:8), churned mechanically speed is 1000 rev/mins, and the power of ultra-sonic dispersion is 60 watts, and drop rate is 1 droplet/minute.The aniline of 2.5mmol is dissolved in the 20ml0.1mol/L hydrochloric acid soln, and the disposable suspension that joins the starch nano micelle that had before made is regulated pH value about 1-2 with hydrochloric acid.3.0mmol iron(ic) chloride is dissolved in the 20m deionized water, slowly is added dropwise in the system, be controlled at and dropwised in 40 minutes, temperature of reaction about 5 ℃, sustained reaction 18 hours.Add the acetone termination reaction, use acetone, distilled water repetitive scrubbing respectively, use the sand core funnel suction filtration,, obtain blackish green product at 60 ℃ of vacuum-drying 24h.The median size of complex microsphere is in 700 nanometers, and room-temperature conductivity is 4.6 * 10
-2S/cm.
Embodiment 3
0.3 gram starch places 10ml N-N N,N-DIMETHYLACETAMIDE, 80 ℃ of lower magnetic force stirring and dissolving.Starch solution slowly is added dropwise to the 100ml deionized water/alcohol mixed solution that contains 0.035 gram hexadecyl benzene sulfonic acid sodium salt, and (alcohol: water=1:9), churned mechanically speed is 1000 rev/mins, and the power of ultra-sonic dispersion is 60 watts, and drop rate is 1 droplet/minute.The aniline of 2.5mmol is dissolved in the 20ml 0.1mol/L phosphoric acid solution, and the disposable suspension that joins the starch nano micelle that had before made uses phosphoric acid regulating ph value about 2-3.The 1.25mmol potassium bichromate is dissolved in the 20mL deionized water, slowly is added dropwise in the system, be controlled at and dropwised in 40 minutes, temperature of reaction about 5 ℃, sustained reaction 12 hours.Add the acetone termination reaction, use acetone, distilled water repetitive scrubbing respectively, use the sand core funnel suction filtration,, obtain blackish green product at 60 ℃ of vacuum-drying 24h.The median size of complex microsphere is in 740 nanometers, and room-temperature conductivity is 7.9 * 10
-3S/cm.
Embodiment 4
0.25 gram starch places the 10ml dimethyl sulfoxide (DMSO), 60 ℃ of lower magnetic force stirring and dissolving.Starch solution slowly is added dropwise to the 100ml deionized water/alcohol mixed solution that contains 0.02 gram naphthene sulfonic acid, and (alcohol: water=1:19), churned mechanically speed is 1000 rev/mins, and the power of ultra-sonic dispersion is 60 watts, and drop rate is 1 droplet/minute.The aniline of 2.5mmol is dissolved in the 20ml 2mol/L acetum, and the disposable suspension that joins the starch nano micelle that had before made is regulated pH value about 2-3 with acetum.Get 0.255ml superoxol (30%wt) and be mixed with 20ml solution, slowly be added dropwise in the system, be controlled at and dropwised in 40 minutes, temperature of reaction about 5 ℃, sustained reaction 18 hours.Add the acetone termination reaction, use acetone, distilled water repetitive scrubbing respectively, use the sand core funnel suction filtration,, obtain blackish green product at 60 ℃ of vacuum-drying 24h.The median size of complex microsphere is in 620 nanometers, and room-temperature conductivity is 1.7 * 10
-4S/cm.
Embodiment 5
0.1 gram starch places the 10ml N,N-dimethylacetamide, 80 ℃ of lower magnetic force stirring and dissolving.Starch solution slowly is added dropwise to the 100ml deionized water/alcohol mixed solution that contains 0.025 gram Sodium dodecylbenzene sulfonate, and (alcohol: water=1:9), churned mechanically speed is 1000 rev/mins, and the power of ultra-sonic dispersion is 60 watts, and drop rate is 1 droplet/minute.The aniline of 2.5mmol is dissolved in the 20ml1.2mol/L tosic acid solution, and the disposable suspension that joins the starch nano micelle that had before made is regulated pH value about 1-2 with tosic acid solution.The 2.5mmol ammonium persulphate is dissolved in the 20m deionized water, slowly is added dropwise in the system, be controlled at and dropwised in 40 minutes, temperature of reaction about 5 ℃, sustained reaction 16 hours.Add the acetone termination reaction, use acetone, distilled water repetitive scrubbing respectively, use the sand core funnel suction filtration,, obtain blackish green product at 60 ℃ of vacuum-drying 24h.The median size of complex microsphere is in 320 nanometers, and room-temperature conductivity is 2.9 * 10
-4S/cm.
Embodiment 6
0.15 gram starch places 10ml N, in the dinethylformamide, 60 ℃ of lower magnetic force stirring and dissolving.Starch solution slowly is added dropwise to the 100ml deionized water/alcohol mixed solution that contains 0.02 gram sodium naphthalene sulfonate, and (alcohol: water=1:9), churned mechanically speed is 1000 rev/mins, and the power of ultra-sonic dispersion is 60 watts, and drop rate is 1 droplet/minute.The aniline of 2.5mmol is dissolved in the 20ml0.1mol/L sulphuric acid soln, and the disposable suspension that joins the starch nano micelle that had before made is regulated pH value about 0-1 with sulphuric acid soln.The 1.25mmol potassium bichromate is dissolved in the 20m deionized water, slowly is added dropwise in the system, be controlled at and dropwised in 40 minutes, temperature of reaction about 5 ℃, sustained reaction 16 hours.Add the acetone termination reaction, use acetone, distilled water repetitive scrubbing respectively, use the sand core funnel suction filtration,, obtain blackish green product at 60 ℃ of vacuum-drying 24h.The median size of complex microsphere is in 580 nanometers, and room-temperature conductivity is 5.6 * 10
-1S/cm.
Embodiment 7
0.2 gram starch places the 10ml dimethyl sulfoxide (DMSO), 60 ℃ of lower magnetic force stirring and dissolving.Starch solution slowly is added dropwise to the 100ml deionized water/alcohol mixed solution that contains 0.03 gram sodium lauryl sulphate, and (alcohol: water=1:9), churned mechanically speed is 1000 rev/mins, and the power of ultra-sonic dispersion is 60 watts, and drop rate is 1 droplet/minute.The aniline of 2.5mmol is dissolved in the 20ml 0.1mol/L hydrochloric acid soln, and the disposable suspension that joins the starch nano micelle that had before made is regulated pH value about 0-1 with hydrochloric acid.The 2.5mmol ammonium persulphate is dissolved in the 20mL deionized water, slowly is added dropwise in the system, be controlled at and dropwised in 40 minutes, temperature of reaction about 5 ℃, sustained reaction 16 hours.Add the acetone termination reaction, use acetone, distilled water repetitive scrubbing respectively, use the sand core funnel suction filtration,, obtain blackish green product at 60 ℃ of vacuum-drying 24h.The median size of complex microsphere is in 490 nanometers, and room-temperature conductivity is 0.16S/cm.
Claims (7)
1. conductive polyanion/starch shell-core type composite microsphere, the kernel that it is characterized in that complex microsphere is a natural polymer starch, and shell is a conductive polymer polyanilinc, and starch is covered by the inside of electrically conductive polyaniline, forms the core-shell type complex microsphere.
2. conductive polyanion/starch shell-core type composite microsphere according to claim 1 is characterized in that described core-shell type complex microsphere particle diameter in 50 nanometers～5 micron, and room-temperature conductivity is 1.5 * 10
-5～1.6S/cm.
3. the preparation method of a kind of conductive polyanion/starch shell-core type composite microsphere according to claim 1 is characterized in that comprising step:
(1) preparation starch nano micelle: get a certain amount of starch solution, under high speed machine stirring and ultra-sonic dispersion situation, dropwise join in the water/alcohol mixeding liquid that contains anion surfactant, wherein, the volume ratio of starch solution and water/alcohol mixeding liquid is 1:10～20;
(2) preparation aniline/doping agent aqueous solution, and join in the starch nano micelle system of step (1) preparation;
(3) to the hanging drop oxidizer aqueous solution of step (2) preparation, at room temperature initiated polymerization obtains described conductive polyanion/starch shell-core type composite microsphere.
4. the preparation method of a kind of conductive polyanion/starch shell-core type composite microsphere according to claim 3, it is characterized in that: the solvent that the preparation starch solution uses is dimethyl sulfoxide (DMSO), N, dinethylformamide, N, the mixed solution of N-N,N-DIMETHYLACETAMIDE or above-mentioned solvent and deionized water, the massfraction of starch is 5%～35% in the solution, stirs down at 40 ℃～90 ℃ and makes it whole dissolvings.
5. the preparation method of a kind of conductive polyanion/starch shell-core type composite microsphere according to claim 3, it is characterized in that: anion surfactant is Witco 1298 Soft Acid and metal-salt, hexadecyl Phenylsulfonic acid and metal-salt, naphthene sulfonic acid and metal-salt thereof or sodium lauryl sulphate, the volume ratio of dehydrated alcohol and deionized water is 1:1.5～9 in water/alcohol mixeding liquid, and churned mechanically speed is 1000～1500 rev/mins.
6. the preparation method of a kind of conductive polyanion/starch shell-core type composite microsphere according to claim 3, it is characterized in that: described doping agent is mineral acid hydrochloric acid, sulfuric acid, perchloric acid, phosphoric acid, nitric acid, or organic acid acetic acid, tosic acid, the pH value of system is 0～3.
7. the preparation method of a kind of conductive polyanion/starch shell-core type composite microsphere according to claim 3, it is characterized in that: described oxygenant is ammonium persulphate, hydrogen peroxide, potassium bichromate, potassium hypochlorite, clorox or iron(ic) chloride, polymerization temperature is 5～30 ℃, polymerization time is 5～24 hours, and the mol ratio of aniline monomer and oxygenant is 1:1～2.
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Cited By (2)
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| CN102949971A (en) * | 2012-10-30 | 2013-03-06 | 中科院广州化学有限公司 | Starch base silica composite microspheres, preparation method and applications thereof |
| CN108396561A (en) * | 2018-04-10 | 2018-08-14 | 天津工业大学 | A kind of core-shell structural conductive nanofiber and preparation method thereof |
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| CN101173056B (en) * | 2007-10-16 | 2010-05-19 | 厦门大学 | Method for producing verelite microsphere for surface decoration of conductive polyaniline nano-wire |
| CN101215385B (en) * | 2008-01-16 | 2010-06-23 | 西南大学 | Process for preparing nano-starch powder |
| EP2246366A1 (en) | 2009-03-24 | 2010-11-03 | Mondi Limited South Africa | Process and device for preparing starch microgel particles for the paper industry |
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| CN102492139A (en) * | 2011-12-06 | 2012-06-13 | 天津大学 | Polyaniline nanometer microsphere prepared with solution method and method thereof |
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102949971A (en) * | 2012-10-30 | 2013-03-06 | 中科院广州化学有限公司 | Starch base silica composite microspheres, preparation method and applications thereof |
| CN108396561A (en) * | 2018-04-10 | 2018-08-14 | 天津工业大学 | A kind of core-shell structural conductive nanofiber and preparation method thereof |
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